Insecticidal pyrethroid compositions

ABSTRACT

This invention relates to novel insecticidal compositions comprising a m-phenoxybenzyl ester of a spirocarboxylic acid and an insecticidal agent of chlorinated camphene; O,O-dimethyl-O-p-nitrophenyl phosphorothioate; N&#39;-(4-chloro-o-tolyl)-N,N-dimethylformamidine; 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane; O,O-dimethyl-S-[4-oxo-1,2,3-benzotriazin-3-(4H)-ylmethyl]phosphorodithioate; 1-naphthyl N-methylcarbamate. O,O-dimethylphosphorodithioate of diethylmercaptosuccinate; or mixtures of the latter named chemical insecticidal agents and to the use of the above compositions for protecting agricultural crops from attack by insect pests.

This is a division, of application Ser. No. 874,305, filed Feb. 2, 1978 now abandoned, which in turn is a division of Ser. No. 623,864 filed Oct. 20, 1975, now U.S. Pat. No. 4,087,523 (1978).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The field of the invention is pyrethroids in combination with selected insecticidal agents for the control of insect pests, particularly those which are of major economic importance to the cotton industry.

2. The Prior Art

Pyrethrin-like compounds (pyrethroids) are known in the chemical art. Many such compounds have been shown to possess insecticidal properties, but most have failed to provide entirely satisfactory insect and/or acarina control. None, to the best of our knowledge, has been entirely satisfactory for the control of the complex of insects which ravage growing cotton plants: and, with few exceptions, all have been subject to extremely rapid degradation to non-toxic substances. This latter property has been recognized as a major deficiency of the pyrethroids. While such compounds have provided excellent knockdown of many insects, rapid degradation of said compounds has resulted in lack of residual insect control even for a few days.

The pyrethroids useful in my invention are described in the R. W. Addor United States Patent Application Ser. No. 550,105, filed Feb. 13, 1975. now U.S Pat. No. 3,966,959.

Heretofore, many conventional insecticidal chemicals have also been employed for the control of insects which ravage growing cotton plants. Many have met with a high degree of acceptance by cotton growers, but virtually all have been found to have their limitations and none has afforded complete protection for the growing cotton plants against the insect complex encountered.

It is therefore an object of the present invention to provide an insecticidal composition which is highly effective for protecting crops, particularly cotton crops, from insect attack.

It is also an object of this invention to provide a chemical composition which contains (1) a pyrethroid compound that is not subject to immediate degradation and (2) a selected phosphate, N-methylcarbamate, chlorinated camphene or chlorinated formamidine insecticide; and it is a further object of this invention that such composition be more effective for controlling certain Lepidopterous, Hemipterous and Coleopterous insects and more effective for protecting important agronomic crops from attack by the insects, than is the pyrethroid alone or the phosphate, carbamate, chlorinated camphene, chlorinated formamidine or mixtures thereof.

Advantageously, the compositions of the invention are useful as contact or stomach posions. They are superior in insecticidal activity or insect repellancy, to the pyrethroid alone or the phosphate, carbamate, chlorinated camphene or chlorinated formamidine insecticides and can be employed as protecting agents for important agronomic crops such as cotton, soybeans, tobacco, cole crops, leafy vegetables, forage crops, corn, snapbeans, and tomatoes.

SUMMARY OF INVENTION

This invention relates to insecticidal compositions comprising (a) a phenoxybenzyl ester of a spirocarboxylic acid having a formula of: ##STR1## wherein R₁ is hydrogen, cyano or ethylnyl, represents a single or double bond, and the optical and geometric isomers thereof, and (b) chlorinated camphene; 0,0-dimethyl-0-p-nitrophenyl phosphorothioate; N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine; 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane; 0,0-dimethyl S-[4-oxo-1,2,3-benzotriazin-3-(4H)yl-methyl]phosphorodithioate; 0,0-dimethylphosphorodithioate of diethylmercaptosuccinate; 1-naphthyl N-methylcarbamate, and mixtures thereof. More particularly, this invention relates to novel insecticidal compositions in which the ratio of the conventional insecticide to the pyrethroid is from 5:4 to 40:1 and preferably 5:4 to 20:1. Still more particularly, the compositions of this invention are applied to foliage of plants, which are to be protected from insect attack, in amounts sufficient to provide from about 1.0 to 5.0 oz and preferably 1.6 to 3.2 oz of the pyrethroid and from 0.25 to 4.0 lbs per acre of the conventional insecticide. These most preferred rates are equivalent to 0.11 to 0.22 kg/hectare of the pyrethroid and from 0.28 to 4.48 kg/hectare of the conventional insecticide.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with this invention the phenoxybenzyl esters of benzospirocarboxylic acids depicted by formula I, can be prepared by reacting approximately equimolar amounts of an acid halide, preferably the chloride, of a benzospirocarboxylic acid (IV) and m-phenoxybenzyl alcohol (V). The reaction is generally conducted in the presence of a suitable solvent such as benzene, toluene, diethyl ether, or the like, at a temperature between about 10° C. and 30° C., and in the presence of an acid acceptor such as an organic tertiaryamine such as triethylamine, trimethylamine, pyridine, or the like. The reaction can be graphically illustrated as follows: ##STR2## wherein R₁ is hydrogen, cyano, or ethynyl, and X is halogen, preferably chloro.

The benzospirocarboxylic acid halide (IV) is readily obtained by reaction of the appropriate benzospirocarboxylic acid (III) with a thionyl halide such as thionyl chloride, thionyl bromide or a phosphorus halide such as phosphorus trichloride or phosphorus pentachloride in the presence of an organic solvent such as toluene, benzene or benzenehexane mixture. This reaction may be conducted at room temperature but is preferably conducted at 60°-90°; and can be illustrated as follows: ##STR3##

The formula II phenoxybenzyl esters of spirocarboxylic acids can be prepared in a manner similar to that described above for the preparation of the formula I benzospiro compounds, by substituting the appropriate spirocarboxylic acid (VI) for the above-mentioned benzospirocarboxylic acid (III); converting said acid to its corresponding acid halide (VII) and reacting the thus-formed acid halide with m-phenoxybenzyl alcohol (V), under the conditions mentioned above, to obtain the formula (II) m-phenoxybenzyl ester of the spirocarboxylic acid. This reaction can be graphically illustrated as follows: ##STR4## wherein X is halogen, preferably chloro, and R₁ is hydrogen, cyano, or ethynyl.

In accordance with this invention, it should also be understood that various geometric isomers as well as optical isomers of the above-identified compounds do result from the preparations described. For example, in the synthesis of the 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic and 2,2-dimethylspiro[2,4]hepta-4-ene-1-carboxylic acid esters of m-phenoxybenzyl alcohol, d and l isomeric pairs are formed. In the preparation of the α-cyano- and α-ethynyl-m-phenoxybenzyl esters, an additonal chiral center is introduced, and this allows for additional d, l pairs. Additionally, the esters derived from 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid will be further complicated by the presence of cis and trans isomers.

For the control of insects, including soil insects, which attack growing plants and/or harvested crops, including stored grain, the insecticidal compositions of this invention may be applied to the foliage of plants, the insect's habitat and/or the insect's food supply. Generally, the active composition is applied in the form of a dilute liquid spray; however, it may also be applied as an aerosol, a dust, wettable powder, or the like.

Liquid sprays which are particularly useful are oil sprays and emulsifiable concentrates which can be further diluted for application.

A typical emulsifiable concentrate useful for protecting a variety of crops such as cereals, cole crops, cucurbits, ornamentals, shrubs, and the like, may comprise about 24% by weight of the active composition; 4% by weight of an emulsifying agent, conventionally employed in the preparation of pyrethroid formulations: 4% by weight of a surfactant; 23% by weight of an organic solvent such as cyclohexanone; and about 45% by weight of a petroleum solvent having a minimum aromatic content of about 93 volume %.

Typical compositions of this invention which are highly effective for controlling insect pests and or protecting crops from attack thereby are as follows.

    __________________________________________________________________________     Typical Preferred Compositions of the Present Invention                                     Rate of Chemical                                                                        *Pyrethroid Rate                                                                        Ratio of Chemical                               Chemical     kg/ha    kg/ha    To Pyrethroid                                   __________________________________________________________________________     Chlorinated Camphene                                                                        2.24-4.48                                                                               0.11-0.22                                                                               10-1 to 40-1                                    Methyl Parathion                                                                            0.28-1.68                                                                               0.11-0.22                                                                               5-4 to 15-1                                     Chlorinated Camphene +                                                                      0.56 to 4.48-                                                                           0.11-0.22                                                                               5-4-1 to                                        Methyl Parathion                                                                            0.28 to 1.68      40-15-1                                         Chlordimeform                                                                               0.56-1.12                                                                               0.11-0.22                                                                               2.5-1 to 10-1                                   Chlorinated Camphene +                                                                      2.2-0.14 0.11-0.22                                                                               10-0.625-1 to                                   Chlordimeform                  20-1.25-1                                       Chlorinated Camphene +                                                                      2.2-0.56- 0.14                                                                          0.11-0.22                                                                               10-2.5-0.625-1                                  Methyl Parathion +                                                             Chlordimeform                  to 20-5-1.25-1                                  Carbaryl     1.12-2.8 0.11-0.22                                                                               5-1 to 25-1                                     Azinphos-methyl                                                                             0.28-0.56                                                                               0.11-0.22                                                                               5-4 to 5-1                                      Melathion    0.56-2.2 0.11-0.22                                                                               2.5-1 to 20-1                                   __________________________________________________________________________      *Preferred pyrethroids are                                                     2,2Dimethyl-4,5-benzospiro[2,4]hepta4,6-diene-1-carboxylic acid,               mphenoxybenzyl ester and                                                       2,2Dimethyl-4,5-benzospiro[2,4]hepta4,6-diene-1-carboxylic acid,               cyano-n-phenoxybenzyl ester.                                             

The invention is further demonstrated by the non-limiting examples provided below.

EXAMPLE 1 Preparation of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, m-phenoxybenzyl ester ##STR5##

To 4.3 g (0.02 mole) of 2,2-dimethyl-4,5-benzospiro-2,4-hepta-4,6-diene-1-carboxylic acid in either hexane/benzene or benzene is added 8 ml of thionyl chloride. The solution is then stirred for 12 hours at room temperature. The solvent is then removed in vacuo leaving 4.7 g of an orange liquid (theoretical yield). Infrared indicates an acid chloride carbonyl at 1790 cm⁻¹.

The acid chloride and 4.0 g (0.02 mole) of m-phenoxy benzyl alcohol are dissolved in 20 ml of ether, and 2.1 g (0.02 mole) of triethylamine dissolved in 8 ml of ether is added dropwise at 20° C. Solids precipitate from solution immediately. The resulting mixture is stirred for 12 hours at room temperature. The crude product is partitioned in an ether/water mixture, and the ether layer is dried over magnesium sulfate and concentrated in vacuo to yield 7.7 g (96% theory) of a brown liquid.

The crude product is purified by dry-column chromatography on silica gel using 25% methylene chloride in hexane as a solvent. 4.4 Grams of a pale yellow liquid is obtained. The infrared spectrum shows an ester carbonyl band at 1720 cm⁻¹. The nuclear magnetic resonance spectrum (CCl₄) shows the following: δ=1.41, 1.45, 1.58, 1.66 (4S, 6H, methyls), 2.61 (S, 1H, cyclopropane H), 4.85-5.10 (m, 2H, O--CH₂), 6.12 (d, 0.5H, J=5.5 Hz, vinyl), 6.66-7.76 (m, 14.5H aromatic and vinyl).

Analyses: Calculated for C₂₇ H₂₄ O₃ : C, 81.83; H, 6.06. Found: C, 82.14; H, 6.29.

EXAMPLE 2 Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester ##STR6##

2,2-Dimethyl-4,5-benzospiro [2,4] hepta-4,6-diene-1-carboxylic acid, 3.4 g, is dissolved in 100 ml of a hexane/benzene (4:1) solution. Thionyl chloride, 15.0 g, is then added and the solution is stirred for 12 hours. Refluxing is carried out for 20 minutes, and the volume is reduced in vacuo to remove solvents and excess thionyl chloride. The acid chloride is used directly without further purification. The acid chloride is taken up in 20 ml of benzene and is added dropwise to a solution of 3.1 g of α-cyano-m-phenoxybenzyl alcohol and 1.0 g of pyridine in 100 ml of benzene. After 4 hours, the precipitate is filtered, and the filtrate reduced in vacuo to give a viscous oil. Purification by column chromatography on silica gel with elution by chloroform/hexane (1:2) gives 1.3 g of pale yellow oil which exhibits the following spectral properties: infrared spectrum (neat film) 1730 cm⁻¹ ; nuclear magnetic resonance spectrum (CDCl₃) δ= 6.8-7.6 (m, 14.5H, aromatic and vinyl), 6.37 (m, 1H, ##STR7## 6.22 (d, 0.5H, vinyl), 2.73 (m, 1H, ##STR8## 1.72-1.43 (m, 6H, methyls).

EXAMPLE 3 Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid, m-phenoxybenzyl ester

The procedure of Example 1 is followed using 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product as an oil. The pure ester obtained by chromatography had the following spectral properties: Infrared spectrum (heat film) 1720 cm⁻¹ ; nuclear magnetic resonance spectrum (CCl₄) δ=6.7-7.6 (m, 13H, aromatic), 4.8-51 (m, 2H, O--CH₂), 1.1-3.2 (m, 11H, CH₃, indane CH₂, and cyclopropane H).

EXAMPLE 4 Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester

The procedure of Example 2 is followed using 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product.

EXAMPLE 5 Preparation of 2,2-Dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid, m-phenoxybenzyl ester

The procedure of Example 1 is followed using 2,2-dimethyl[2,4]hepta-4,6-diene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product.

EXAMPLE 6 Preparation of 2,2-Dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester

The procedure of Example 2 is followed using 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product.

EXAMPLE 7 Preparation of 2,2-Dimethylspiro[2,4]heptane-1-carboxylic acid, m-phenoxybenzyl ester ##STR9##

The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]heptane-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product. The pure ester obtained by chromatography has the following spectral properties: Infrared spectrum (neat film) 1730 cm⁻¹ ; nuclear magnetic resonance spectrum (CCl₄) δ=6.8-7.4 (m, 9H, aromatic), 5.0 (s, 2H, O--CH₂), 1.4-1.7 (m, 8H, cyclopentane CH₂), 1.1 (s, 3H, CH₃), 1.2 (s, 3H, CH₃).

EXAMPLE 8 Preparation of 2,2-Dimethylspiro[2,4]heptane-1-carboxylic acid, α-cyano-m-phenoxybenzyl ester

The procedure of Example 2 is followed using 2,2-dimethylspiro[2,4]heptane-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid to give the crude product.

It must be recognized that various geometric isomers as well as optical isomers result from these preparations. Thus, in the case of the 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid and 2,2-dimethylspiro[2,4]heptane-1-carboxylic acid esters of m-phenoxybenzyl alcohol, d and l isomeric pairs will result. Where the α-cyano and α-ethynyl m-phenoxybenzyl esters are formed, an additional chiral center is introduced allowing for additional d, l pairs. Although in most instances the separation of these isomers may not be practical, it is recognized that they will differ in the degree of effectiveness and the spectrum of their activity against the many insects and other pests of economic importance. In addition, the subject esters derived from 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and 2,2-dimethyl-4,5-benzospiro[2,4]-hepta-4-ene-1-carboxylic acid will be further complicated by the presence of cis and trans isomers. These different esters are also expected to show differing degrees of insecticidal activity when separately tested.

EXAMPLE 9 Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl ester

The procedure of Example 1 is followed using α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

EXAMPLE 10 Preparation of 2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl

The procedure of Example 1 is followed using 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4-ene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

EXAMPLE 11 Preparation of 2,2-Dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl ester

The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]hepta-4,6-diene-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

EXAMPLE 12 Preparation of 2,2-Dimethylspiro[2,4]heptane-1-carboxylic acid, α-ethynyl-m-phenoxybenzyl ester

The procedure of Example 1 is followed using 2,2-dimethylspiro[2,4]heptane-1-carboxylic acid in place of 2,2-dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-carboxylic acid and α-ethynyl-m-phenoxybenzyl alcohol in place of m-phenoxybenzyl alcohol to give the product as an oil.

EXAMPLE 13 Evaluation of Chemical Compositions Against Tobacco Budworm (Heliothis virescens) on Cotton Plants

The effectiveness of the compositions of this invention for protecting cotton plants, and/or controlling insects which attack them, is demonstrated by the following tests.

In these tests stock solutions of test compounds are prepared by dissolving and/or dispersing a sufficient amount of test compound in 67 ml of acetone and diluting the thus prepared solution with 36 ml of water to yield 100 ml of stock solution with a given concentration of test compound. Thus, 400 mg of N'-(4-chloro-2-methylphenyl)-N,N-dimethylformamidine yields a stock solution containing 4,000 ppm of compound; and this solution, when used with equal parts of three additional stock solutions, provides an insecticidal composition containing 1,000 ppm of the above-said compound. All stock solutions of test compounds are prepared in this manner and solutions are varied in concentration to match the desired ratio among components.

To determine the effectiveness of test compositions for controlling the tobacco budworm (Heliothis virescens (Fabricius)) and protecting cotton plants from attack thereby, one-third of a cotyledon of a Stoneville #213 cotton plant, which had been dipped in test solution is placed in a 1 oz plastic medicine cup containing a 1 inch dental wick saturated with water. One third-instar tobacco budworm larva is placed in each cup and the cup capped and held at 26° C. and 30% relative humidity. Ten larvae are used for each concentration tested. After 3 days, mortality counts are made. Data obtained are reported below.

For convenience in reporting data obtained in this evaluation and/or evaluations reported in subsequent examples, common names for chemicals other than the pyrethroids are used. Said chemicals are as follows:

    ______________________________________                                         Chemical              Common Name                                              ______________________________________                                         Chlorinated camphene  toxaphene                                                O,O-Dimethyl-S-[4-oxo-1,2,3-                                                                         azinphos-methyl                                          benzotriazin-3(4H)-ylmethyl]-                                                  Phosphorodithioate                                                             N'-(4-Chloro-2-methylphenyl)-                                                                        chlordimeform                                            N,N-dimethylformamidine                                                        O,O-Dimethyl-O-p-nitrophenyl                                                                         methyl parathion                                         phosphorothioate                                                               2-(Diethoxyphosphinylimino)-                                                                         mephosfolan                                              4-methyl-1,3-dithiolane                                                        O,O-Dimethyl phosphorodithioate                                                                      malathion                                                of diethylmercaptosuccinate                                                    1-Naphthyl N-methylcarbamate                                                                         carbaryl                                                 ______________________________________                                    

                  TABLE I                                                          ______________________________________                                         Control of Tobacco Budworm Larvae on                                           Cotton Plants Expressed                                                        as Percent Mortality of Larvae                                                                          Concen-  %                                                                     tration  Mor-                                            Compound              ppm      tality                                       ______________________________________                                         2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-                                                        15           10                                       1-carboxylic acid, m-phenoxybenzyl ester                                                                30           33                                       2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-                                                        30           38                                       1-carboxylic acid, α-cyano-                                              m-phenoxybenzyl ester                                                          Chlorinated camphene     100          0                                        Chlordimeform            1000         50                                       Azinphos-methyl          50           0                                        Chlorinated camphene plus - 2,2-Dimethyl-4,5-                                                           100                                                   benzospiro[2,4]hepta-4,6-diene-1-carboxylic                                                             plus         50                                       acid, m-phenoxybenzyl ester                                                                             30                                                    Chlorinated camphene plus 2,2-Dimethyl-4,5-                                                             60                                                    benzospiro[2,4]hepta-4,6-diene-1-carboxylic                                                             plus         100                                      acid, α-cyano-m-pheoxybenzyl ester                                                                3                                                     Aminophos-methyl plus 2,2 Dimethyl-4,5-                                                                 50                                                    benzospiro[2,4]hepta-4,6-diene-1-carboxylic                                                             plus         80                                       acid, α-cyano-m-phenoxybenzyl ester                                                               15                                                    ______________________________________                                    

EXAMPLE 14 Evaluation of Chemical Compositions Against Cabbage Looper (Trichoplusia ni) larvae on Cotton Plants

To determine the effectiveness of test compositions for controlling cabbage looper (Trichoplusia ni (Huber)) on cotton plants true leaves of a Stoneville #213 cotton plant, dipped in test solution and dried, are placed in separate 9.0 cm petri dishes which are fitted with a moist Whatman #1 filter paper. Ten third-instar cabbage looper larvae are placed in each of the dishes which are then covered and held in a room maintained at 26° C. and 30% relative humidity. After 3 days, mortality counts are made and feeding damage is estimated. Data obtained are reported below.

                  TABLE II                                                         ______________________________________                                         Control of Cabbage Looper Larvae on                                            Cotton Plants Expressed as Percent Mortality and                               Plant Protection Expressed as Percent Feeding Damage                                             Concen-           %                                                            tration  %        Feeding                                    Compound or Composition                                                                          ppm      Mortality                                                                               Damage                                     ______________________________________                                         2,2-Dimethyl-4,5-benzospiro [2,4]-                                                               5            20     30                                       hepta-4,6-diene-1-carboxylic acid,                                                               3            15     63                                       m-phenoxybenzyl ester                                                                            1.5           0     100                                      2,2-Dimethyl-4,5-benzospiro[2,4]-                                                                1.5          60     10                                       hepta-4,6-diene-1-carboxylic acid,                                                               1            68     16                                       α-cyano-m-phenoxybenzyl ester                                            Chlorinated camphene                                                                             100           0     100                                      Methyl parathion   10           0     100                                      Chlordimeform     1000         40     100                                      Aminphos-methyl   150           0     100                                      4-(diethoxyphosphinylimino)-4-                                                                   100          50     100                                      methyl-1,3-dithiolane                                                          2,2-Dimethyl-4,5-benzospiro[2,4]                                                                 3                                                            hepta-4,6-diene-1-carboxylic acid,                                                               plus         70     10                                       m-phenoxybenzyl ester plus                                                                       10                                                           methyl parathion                                                               2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             m-phenoxybenzyl ester                                                                            1                                                            Plus              Plus                                                         Methyl parathion  15                                                           Plus              Plus         90     2                                        Chlordimeform     1.875                                                        Plus              Plus                                                         Chlorinated camphene                                                                             30                                                           2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             α-cyano-m-phenoxybenzyl ester                                                              1                                                            Plus              Plus         100    1                                        Chlordimeform     1000                                                         2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             m-phenoxybenzyl ester                                                                            0.25                                                         Plus              Plus         70     20                                       Chlordimeform     250                                                          Plus              Plus                                                         Chlorinated camphene                                                                             125                                                          2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             α cyano-m-phenoxybenzyl ester                                                              1.5                                                          Plus              Plus         90     5                                        Aminphos-methyl   150                                                          2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             m-phenoxybenzyl ester                                                                            5                                                            Plus              Plus         90     5                                        Aminphos-methyl   150                                                          2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             α-cyano-m-phenoxybenzyl ester                                                              1                                                            Plus              Plus         90     5                                        2-(diethoxyphosphinylimino)-4-                                                                   100                                                          methyl-1,3-dithiolane                                                          ______________________________________                                    

EXAMPLE 15 Effectiveness of Chemical Compositions Against Adult Boll Weevils (Anthonomus grandis) on Cotyledons of Cotton Plants

To determine the effectiveness of test compositions for controlling boll weevils and/or protecting plants from their attack, cotyledons from Stoneville #213 cotton plants are dipped in solutions of test compositions and then permitted to dry. After drying, these treated cotyledons are placed in individual 9.0 cm petri dishes with moist Whatman #1 filter papers on the bottom thereof. Ten adult boll weevils are then placed in each of the dishes and the dishes are covered and placed in a room maintained at 26° C. and 30% relative humidity. After 3 days, mortality counts are made and the amount of feeding is estimated.

Data obtained are reported in the Table III below.

                  TABLE III                                                        ______________________________________                                         Effectiveness of Compositions for                                              Controlling Adult Boll Weevils                                                 on Cotyledons of Cotton Plants                                                                     Concen-  %      %                                                              tration  Mor-   Feeding                                    Compound of Composition                                                                            ppm      tality Damage                                     ______________________________________                                         2,2-Dimethyl-4,5-benzospiro                                                                        300          43   5                                        [2,4]hepta-4,6-diene-1-carboxylic                                                                  100          23   3                                        acid, m-phenoxybenzyl ester                                                    Chlorinated camphene                                                                               500          20   10                                                           100           0   15                                       2,2-Dimethyl-4,5-benzospiro[2,4]-                                              hepta-4,6-diene-1-carboxylic acid,                                             α-cyano-m-phenoxybenzyl ester                                                                100          32   3                                        Methyl parathion    3            20   25                                       Chlordimeform       1000          0   25                                       Malathion           100          30   30                                       Chlorinated camphene plus 2,2-                                                 Dimethyl-4,5-benzospiro[2,4]-                                                                      100                                                        hepta-4,6-diene-1-carboxylic                                                                       Plus         50   0                                        acid, α-cyano-m-phenoxybenzyl                                                                100                                                        ester                                                                          Methyl parathion plus 2,2-Dimethyl-                                            4,5-benzospiro[2,4]hepta-4,6-                                                                      3                                                          diene-1-carboxylic acid, α-cyano                                                             +            100  5                                        m-phenoxybenzyl ester                                                                              100                                                        Chlorinated camphene plus methyl                                                                   60                                                         Parathion plus 2,2-Dimethyl-4,5-                                                                   +                                                          benzospiro[2,4]hepta-4,6-diene-1-                                                                  30           100  0                                        carboxylic acid, m-phenoxybenzyl                                                                   +                                                          ester               100                                                        Chlorinated camphene plus methyl                                                                   60                                                         parathion plus 2,2-Dimethyl-4,5-                                                                   +                                                          benzospiro[2,4]hepta-4,6-diene-1-                                                                  30           100  0                                        carboxylic acid, α-cyano-m-phenoxy-                                                          +                                                          benzyl ester        100                                                        Chlordimeform plus 2,2-Dimethyl-4,5-                                                               1000                                                       benzospiro[2,4]hepta-4,6-diene-1-                                                                  +                                                          carboxylic acid, m-phenoxybenzyl                                                                   300          90   0                                        water plus chlorinated camphene                                                                    +                                                                              500                                                        Malathion plus 2,2-Dimethyl-4,5-                                                                   100                                                        benzospiro[2,4]hepta-4,6-diene-1-                                                                  +            80   0                                        carboxylic acid, m-phenoxybenzyl                                                                   300                                                        ester                                                                          ______________________________________                                    

EXAMPLE 16 Evaluation of Chemical Compositions for the Control of Western Potato Leaf Hopper (Empoasca abrupta Delong)

A treated primary leaf of a Sieva lima bean plant is placed in a 9.0 cm petri dish with moist Whatman #1 filter paper on the bottom. Approximately 3 to 10, second-instar nymphs are tapped from the culture plant into the test dish which is then covered. The dish is held at about 26° C. and 30% relative humidity for 3 days and then mortality counts are made.

Data obtained are reported in Table IV below.

                  TABLE IV                                                         ______________________________________                                         Effectiveness of Test Compositions for                                         Controlling Western Potato Leaf Hoppers                                                                Concen-  %                                                                     tration  Mor-                                          Chemical or Composition ppm      tality                                        ______________________________________                                         Chlorinated camphene    30           15                                        Methyl Parathion        3            38                                        Azinphos-methyl         5             0                                        2,2-Dimethyl-4,5-benzospiro[2,4]hepta-                                         4,6-diene-1-carboxylic acid, m-phenoxy                                                                 10           46                                        benzyl ester                                                                   2,2-Dimethyl-4,5-benzospiro[2,4]hepta-                                         4,6-diene-1-carboxylic acid, α-cyano-                                                            10           52                                        m-phenoxybenzyl ester                                                          Chlorinated camphene plus 2,2-dimethyl-                                                                30                                                     4,5-benzospiro[2,4]hepta-4,6-diene-1-                                                                  +            85                                        carboxylic acid, m-phenoxybenzyl ester                                                                 10                                                     Chlorinated camphene plus 2,2-Dimethyl-                                        4,5-benzospiro[2,4]hepta-4,6-diene-1-                                                                  10                                                     carboxylic acid, α-cyano-m-phenoxybenzyl                                                         +            100                                       ester                   3                                                      Chlorinated camphene plus                                                                              15                                                     Methyl Parathion plus   +                                                      Chlordimeform plus      7.5          100                                       2,2-Dimethyl-4,5-benzospiro[2,4]hepta-                                                                 +                                                      4,6-diene-1-carboxylic acid,                                                                           0.94                                                   m-phenoxybenzyl ester   +                                                                              5                                                      Azinphos methyl plus 2,2-Dimethyl-4,5-                                                                 1.5                                                    benzospiro[2,4]hepta-4,6-diene-1-carboxylic                                                            +            100                                       acid, α-cyano-m-phenoxybenzyl ester                                                              5                                                      ______________________________________                                    

EXAMPLE 17 Evaluation of Chemical Composition for the control of Bean Aphids (Aphid fabae Scopoli)

A two-inch square fiber pot containing a nasturtium plant which is infested with approximately 100 aphids 2 days prior to test initiation, is placed on a 4 rpm turntable located in an exhaust hood. The plant and aphids are sprayed directly with the test solution for 2 revolutions of the turntable with a DeVilbiss atomizer at 20 psi air pressure. The spray tip is held 6 to 8 inches from the plant during spraying and after spraying the pot with plant and aphids is laid on its side on a white enamel tray. One day after treatment the plants are examined and mortality counts are made. Data obtained are reported in Table V below.

                                      TABLE V                                      __________________________________________________________________________     Effectiveness of Chemical Composition for Controlling Bean Apids (Aphid        fabae Scopoli)                                                                 Chemical or Composition  Concentration ppm                                                                        % Mortality                                 __________________________________________________________________________     Chlorinated camphene     30        30                                          Methyl parathion         1         50                                          Chlorodimeform           100        5                                          Azinphos-methyl          1.5       60                                          Carbaryl                 1.0        0                                          2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-                                                      1.0       51                                          carboxylic acid, m-phenoxybenzyl ester                                                                  0.3        7                                          2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene-1-                                                      0.1       61                                          carboxylic acid, α-cyano-m-phenoxybenzyl ester                                                    0.03      12                                          Chlorinated camphene plus the m-phenoxybenzyl                                                           20                                                    ester (identified-above) +         95                                                                   1.0                                                   Methyl parathion plus the m-phenoxybenzyl ester                                                         1.0                                                   (identified-above)       +         99                                                                   0.3                                                   Methyl parathion plus the α-cyano-m-phenoxybenzyl                                                 1.0                                                   ester (identified above) +         100                                                                  0.03                                                  Chlorinated camphene plus                                                                               0.6                                                   Methyl parathion plus    +                                                                              0.3       95                                          The m-phenoxybenzyl ester                                                                               +                                                                              1.0                                                   Chlorinated camphene plus                                                                               0.6                                                   Methyl parathion plus    +                                                                              0.3       95                                          The α-cyano-phenoxybenzyl ester                                                                   +                                                                              0.1                                                   Chlorinated camphene plus                                                                               0.6                                                   Methyl parathion plus    +                                                                              0.3                                                   Chlordimeform plus       +         100                                                                  0.04                                                                           +                                                     The α -cyano-m-phenoxybenzyl ester                                                                0.1                                                   Chlorinated camphene plus                                                                               12.5                                                  Chlordimeform plus       +                                                                              25        80                                          The m-phenoxybenzyl ester                                                                               +                                                                              0.25                                                  Chlorodimeform plus      100                                                                            +         100                                         The m-phenoxybenzyl ester                                                                               1.0                                                   Chlorinated camphene plus                                                                               12.5                                                                           +                                                     Chlordimeform plus       25        80                                                                   +                                                     The α-cyano-m-phenoxybenzyl ester                                                                 0.025                                                 Malathion plus           10                                                                             +         95                                          The m-phenoxybenzyl ester                                                                               1.0                                                   Malthion plus            10                                                                             +         100                                         The α-cyano-m-phenoxybenzyl ester                                                                 0.1                                                   Azinphos-methyl plus     1.5                                                                            +         100                                         The α-cyano-m-phenoxybenzyl ester                                                                 0.05                                                  Carbaryl plus            1.0                                                                            +         100                                         The m-phenoxybenzyl ester                                                                               1.0                                                   Carbaryl plus            1.0                                                                            +         90                                          The α-cyano-m-phenoxybenzyl ester                                                                 0.1                                                   __________________________________________________________________________

EXAMPLE 18 Evaluation of Test Compositions for the Control of Southern Armyworms (Spodoptera eridania (Cramer))

A treated primary leaf of a Sieva lima bean plant is placed in a 9.0 cm petri dish with moist Whatman #1 filter paper on the bottom and containing 10, third-instar southern armyworm larvae. The dish is covered and held in a room maintained at 26° C. and 30% relative humidity. After 3 days, all petri dishes are examined and mortality counts are made. Data obtained are reported in Table VI below.

                                      TABLE VI                                     __________________________________________________________________________     Effectiveness of Test Compositions for                                         Controlling Southern Armyworms (Spodoptera eridana)                                                       %     % Feeding                                     Compound of Composition                                                                          Concentration ppm                                                                       Mortality                                                                            Damage                                        __________________________________________________________________________     Chlorinated camphene                                                                             30       40    100                                           Methyl Parathion  10       40    100                                           Chlordimeform     1000     70    55                                            Chlordimeform     300      40    80                                            Carbaryl          30       0     100                                           2,2-Dimethyl-4,5-benzospiro[2,4]-                                                                6        50    50                                            hepta-4,6-diene-1-carboxylic acid,                                                               3        5     80                                            m-phenoxybenzyl ester                                                                            1.5      0     100                                           2,2-Dimethyl-4,5-benzospiro[2,4]hepta-                                                           3        66    12                                            4,6-diene-1-carboxylic acid, α-cyano-                                                      1.5      10    15                                            phenoxybenzyl ester                                                                              1        0     43                                            Chlordimeform plus                                                                               1000                                                         The α-cyano-m-phenoxybenzyl ester                                                          +        100   1                                             (identified-above)                                                                               1                                                            Chlordimeform plus                                                                               250                                                          The m-phenoxybenzyl ester                                                                        +        90    15                                            (identified above) plus                                                                          0.75                                                         chlorinated camphene                                                                             +                                                                              25.0                                                         Chlorinated camphene plus                                                                        30                                                           Methyl parathion plus                                                                            +                                                                              15                                                           Chlordimeform plus                                                                               +                                                                              1.9      100   5                                             The α-cyano-m-phenoxybenzyl ester                                                          +                                                                              3                                                            Malathion plus    100                                                                            +        90    5                                             The α-cyano-m-phenoxybenzyl ester                                                          3                                                            Carbaryl plus     30                                                                             +        100   10                                            The m-phenoxybenzyl ester                                                                        3                                                            __________________________________________________________________________

EXAMPLE 19 Evaluation of Test Compositions for the Control of Tarnished Plant Bug (Lygus lineolaris (Palisot de Beauvois))

A treated primary leaf of a Sieva lima bean plant is placed in an 8 oz waxed cup containing a 2 inch dental wick saturated with water and 10 adult tarnished plant bugs. The cup is covered with a clear plastic lid and held in a room maintained at 26° C. and 30% relative humidity. After 3 days, the leaves in the cups are examined and mortality counts are made. Data obtained are reported in Table VII below.

                                      TABLE VII                                    __________________________________________________________________________     Effectiveness of Test Composition for Controlling Tarnished Plant Bugs         (Lyrus lincolaris (Palisot de Beauvois))                                       Chemical or Composition Concentration ppm                                                                        % Mortality                                  __________________________________________________________________________     Methyl parathion        0.3       40                                           Chlorinated camphene    10        50                                           2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene                                                        30        42                                           1-carboxylic acid, m-phenoxybenzyl ester                                       2,2-Dimethyl-4,5-benzospiro[2,4]hepta-4,6-diene                                                        10        47                                           1-carboxylic acid, α-cyano-m-phenoxybenzyl ester                         Methyl parathion plus   0.3                                                    The m-phenoxybenzyl ester                                                                              +         100                                          (identified above)      30                                                     Chlorinated camphene plus                                                                              1.5                                                    Methylparathion plus    +                                                                              0.75      90                                           The α-cyano-m-phenoxybenzyl ester                                                                +                                                      (identified above)      5                                                      __________________________________________________________________________ 

I claim:
 1. An insecticidal composition comprising (i) from about 0.1 to 3 ppm of a phenoxybenzyl ester of a spirocarboxylic acid having the structural formula: ##STR10## wherein R₁ is hydrogen or cyano and represents a single or double bond, or the optical or geometric isomers thereof, and (ii) from about 1 to 30 ppm of of 1-napthyl-N-methylcarbamate and (iii) an inert diluent.
 2. A composition according to claim 1 wherein the phenoxybenzyl ester of a spirocarboxylic acid has the structural formula I and is 2,2-dimethyl-4,5-benzospiro[2,4] hepta-4,6-diene-1-carboxylic acid, alpha-cyano-m-phenoxybenzyl ester.
 3. A method for the control of insect pests comprising applying to the insects habitat, their food supply or their breeding sites, an insecticidally effective amount of a composition (i) from about 0.1 to 3 ppm of a phenoxybenzyl ester of a spirocarboxylic acid having the structural formula: ##STR11## wherein R₁ is hydrogen or cyano and represents a single or double bond, or the optical or geometric isomers thereof, and (ii) from about 1 to 30 ppm of 1-naphthyl-N-methylcarbamate and (iii) an inert diluent.
 4. A method according to claim 3 for the control of Lepidopterous, Hemipterous and Coleopterous insects wherein the spirocarboxylic acid is 2,2-dimethyl-4,5-benzospiro[2,4] hepta-4,6-diene-1-carboxylic acid, alpha-cyano-m-phenoxybenzyl ester.
 5. A method for the control of insect pests according to claim 3 in cotton crops. 